KR101582005B1 - Latex composition for dip-forming and dip-formed article produced therefrom - Google Patents

Abstract

The present invention relates to a carboxylic acid-modified nitrile-based copolymer latex; And a styrenic polymer emulsifier and a dip molded product produced therefrom, wherein a syneresis time is obtained by mixing a carboxylic acid modified nitrile-based copolymer latex with a styrenic polymer emulsifier There is an effect of reducing the generation of foams as compared with the conventional latex composition in which a surfactant is added, and thus the processability is excellent.

Description

[0001] LATEX COMPOSITION FOR DIP-FORMING AND DIP-FORMED ARTICLE PRODUCED THEREFROM [0002]

The present invention relates to a latex composition for deep molding and a molded article produced from the latex composition, and more particularly, to a method for producing a latex composition for deep molding by mixing a carboxylic acid denatured nitrile-based copolymer latex with a styrenic polymer emulsifier to increase the syneresis time To a latex composition for deep molding comprising a carboxylic acid-modified nitrile-based copolymer latex having an improved processability by decreasing the amount of foam generated compared with conventional surfactants, and a molded article produced therefrom.

The tensile strength and durability of nitrile rubber gloves are important factors in determining the quality of gloves, and the efforts of glove manufacturers to increase them have been in the past.

One of the methods for increasing the tensile strength and durability of the glove is a method of manufacturing gloves through a double dip molding method. However, this method causes a syneresis phenomenon in the molded article produced by the first dip molding, which causes instability of the latex during the second dip molding, so that the tensile strength and the tensile strength of the latex glove . ≪ / RTI >

In addition, when a surfactant is added to the process of producing latex to solve the problem of the syneresis, there is a problem that excessive foaming occurs in the production process. Therefore, much research has been focused on the development of latex compositions for deep molding that can solve the problems of syneresis and the foam caused by the addition of a surfactant, but a latex composition for deep molding satisfying all of the above characteristics has not yet been developed .

SUMMARY OF THE INVENTION Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and it is an object of the present invention to provide a latex composition for deep-forming which can increase the workability of the process due to a long syneresis time.

Another object of the present invention is to provide a latex composition for deep molding which can reduce the occurrence of bubbles by the addition of a surfactant and enhance the workability of the process.

It is still another object of the present invention to provide a molded article produced from the latex composition for deep molding.

The above object of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention provides a rubber composition comprising a carboxylic acid-modified nitrile-based copolymer latex; And a styrene-based polymer emulsifier. The present invention also provides a latex composition for deep-forming molding.

The present invention relates to a rubber composition comprising 90 to 99% by weight of a carboxylic acid-modified nitrile-based copolymer latex comprising a carboxylic acid-modified nitrile-based copolymer having a glass transition temperature of -50 ° C to -15 ° C and an average particle size of 90 nm or more, 1 to 10% by weight of a styrene-based polymer emulsion having a weight average molecular weight within a range of 80 to 150 ° C and a weight average molecular weight of 1,000 to 50,000, 3,000 to 30,000 or 5,000 to 20,000, It is possible to solve the above conventional techniques.

It is possible to increase the syneresis time by preparing the latex composition for dip molding by mixing the carboxylic acid modified nitrile-based copolymer latex and the styrene-based polymer emulsifier as in the present invention, and to provide a foaming agent It is possible to manufacture a molded article having excellent workability in a dip molding operation.

The carboxylic acid-modified nitrile-based copolymer latex composition for dip-molding of the present invention comprises a carboxylic acid-modified nitrile-based copolymer latex; And a styrene-based polymer emulsifier.

The glass transition temperature of the carboxylic acid-modified nitrile-based copolymer constituting the carboxylic acid-modified nitrile-based copolymer latex is from -50 ° C to -15 ° C. As another example, the glass transition temperature of the carboxylic acid-modified nitrile-based copolymer latex may be from -45 ° C to -20 ° C. When the glass transition temperature is in this range, the tensile strength is excellent and the stretched product of the dip-molded product is excellent.

The average particle diameter of the carboxylic acid-modified nitrile-based copolymer latex may be 90 nm or more. As another example, the average particle size of the carboxylic acid-modified nitrile-based copolymer latex may be 90 nm to 200 nm, 100 nm to 180 nm, or 120 nm to 150 nm, and the tensile strength after the production of the dip- Do.

The average particle diameter of the present invention may be a weight average particle diameter.

The glass transition temperature of the styrene-based polymer emulsifier may be 80 ° C or higher. As another example, the glass transition temperature of the styrene-based polymer emulsifier may be 80 ° C to 150 ° C. In this range, the storage stability at room temperature is excellent and the mixing property with latex is excellent when the compound is manufactured.

The latex composition for dip molding of the present invention may be prepared by mixing the carboxylic acid-modified nitrile-based copolymer latex and the styrene-based polymer emulsifier in a ratio of 80:20 to 99.9: 0.1, 85:15 to 99.5: 0.5, or 90:10 to 99: By weight. Improved syneresis time within this range The width is large and the viscosity of the carboxylic acid-modified nitrile-based copolymer latex is low, and the stability is improved.

The latex composition for dip molding comprising the carboxylic acid-modified nitrile-based copolymer latex according to the present invention may further contain a vulcanizing agent, an ionic cross-linking agent, a pigment, a vulcanization catalyst, a filler, a thickener and a pH And at least one additive selected from the group consisting of regulators.

The dip-molded article according to the present invention is characterized in that it is obtained by dipping the latex composition for dip-molding.

Hereinafter, the present invention will be described in more detail.

In the dip-molded article of the present invention, a latex is prepared by adding an emulsifier, a polymerization initiator, a molecular weight modifier, and the like to each monomer constituting the latex, mixing the prepared latex and a styrene-based polymer emulsifier to prepare a carboxylic acid nitrile latex composition , And the resulting product is dipped into a final product.

Hereinafter, the carboxylic acid-modified nitrile-based copolymer latex, the styrene-based polymer emulsifier and the latex composition for dip molding, which are used to obtain the dip-shaped article of the present invention, will be described in detail.

1. Carboxylic acid-modified nitrile-based copolymer latex

The carboxylic acid-modified nitrile-based copolymer constituting the carboxylic acid-modified nitrile-based copolymer latex may be mixed with a mixture of a conjugated diene monomer, an ethylenically unsaturated nitrile monomer and an ethylenic unsaturated acid monomer with an emulsifier, a polymerization initiator, And other additives to prepare emulsion polymerization.

The conjugated diene-based monomer as one monomer constituting the carboxylic acid-modified nitrile-based copolymer may be 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2- , 3-pentadiene, and isoprene. Of these, 1,3-butadiene and isoprene are preferable, and 1,3-butadiene is most preferably used. The conjugated diene monomer includes, for example, 40 to 89% by weight, 45 to 80% by weight or 50 to 78% by weight of the total monomers constituting the carboxylic acid-modified nitrile-based copolymer. Within this range, the dip-molded article becomes more flexible and comfortable, and the oil resistance and tensile strength of the dip-molded article are excellent.

The ethylenically unsaturated nitrile-based monomer as the other monomer constituting the carboxylic acid-modified nitrile-based copolymer is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile,? -Cyanonetyl acrylonitrile Acrylonitrile and methacrylonitrile are preferable, and acrylonitrile and acrylonitrile are most preferably used. Of these, acrylonitrile and methacrylonitrile are preferable. The ethylenically unsaturated nitrile-based monomer includes 10 to 50% by weight, 15 to 45% by weight or 20 to 40% by weight of the total monomers constituting the carboxylic acid-modified nitrile-based copolymer. Within this range, the dip-molded article has excellent oil resistance and tensile strength, the dip-molded article is flexible, and the fit feeling is good.

The ethylenic unsaturated acid monomer as another monomer constituting the carboxylic acid-modified nitrile-based copolymer is an ethylenically unsaturated monomer containing at least one acidic group selected from the group consisting of a carboxyl group, a sulfonic acid group and an acid anhydride group, , Ethylenically unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid; Polycarboxylic anhydrides such as maleic anhydride and citraconic anhydride; Ethylenically unsaturated sulfonic acid monomers such as styrenesulfonic acid; Ethylenic unsaturated polycarboxylic acid partial ester monomers such as monobutyl fumarate, monobutyl maleate, mono-2-hydroxypropyl maleate, and the like. Of these, methacrylic acid is particularly preferable. Such ethylenically unsaturated acid monomers can be used in the form of alkali metal salts or ammonium salts. The ethylenically unsaturated acid monomer is contained in an amount of 0.1 to 10% by weight, 0.5 to 9% by weight or 1 to 8% by weight of the total monomers constituting the carboxylic acid-modified nitrile-based copolymer. Within this range, the tensile strength of the dip-molded article is excellent, the dip-molded article is flexible, and the wearing feeling is good.

The carboxylic acid-modified nitrile-based copolymer may further include another ethylenic unsaturated monomer copolymerizable with the monomers, for example, a vinyl aromatic monomer selected from the group consisting of styrene, alkylstyrene, and vinylnaphthalene; Fluoroalkyl vinyl ethers such as fluoro ethyl vinyl ether; (Meth) acrylamide, N, N-dimethylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide and N-propoxymethyl An ethylenically unsaturated amide monomer selected from the group consisting of: Nonconjugated diene monomers such as vinylpyridine, vinylnorbornene, dicyclopentadiene and 1,4-hexadiene; (Meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, trifluoroethyl (Meth) acrylate, dibutyl fumarate, diethyl maleate, methoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, cyanomethyl Ethyl (meth) acrylate, 2-ethyl-6-cyanohexyl (meth) acrylate, 3-cyanopropyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxy An ethylenically unsaturated carboxylic acid ester monomer selected from the group consisting of glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and glycidyl (meth) acrylate. The amount of the other copolymerizable ethylenically unsaturated monomer to be used is, for example, the total amount of the mixture of the conjugated diene monomer, the ethylenically unsaturated nitrile monomer, and the ethylenic unsaturated acid monomer as the total monomer mixture constituting the carboxylic acid modified nitrile- And more preferably within a range of 15 to 25% by weight. Within this range, soft feeling and tensile strength are balanced.

The emulsifier is not particularly limited, and for example, an anionic surfactant, a nonionic surfactant, a cationic surfactant, and a positive surfactant can be used. Of these, anionic surfactants selected from the group consisting of alkylbenzenesulfonic acid salts, aliphatic sulfonic acid salts, sulfuric acid ester salts of higher alcohols,? -Olefin sulfonic acid salts and alkyl ether sulfuric acid ester salts are particularly preferably used. The amount of the emulsifier used is, for example, from 0.3 to 10 parts by weight, from 0.8 to 8 parts by weight, or from 1.5 to 6 parts by weight based on 100 parts by weight of the monomer constituting the carboxylic acid-modified nitrile-based copolymer. Within this range, it is possible to reduce the problem that the stability in polymerization is excellent and the production of the deep-formed product becomes difficult due to the increase of foaming.

The polymerization initiator is not particularly limited, but a radical initiator can be used. Examples of the radical initiator include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium persulfate, and hydrogen peroxide; t-butyl peroxide, cumene hydroperoxide, p-methane hydroperoxide, di-t-butyl peroxide, t-butyl cumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, Organic peroxides such as oxides, 3,5,5-trimethylhexanol peroxide, t-butyl peroxyisobutyrate; At least one selected from the group consisting of azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile and azobisisobutyric acid (butyl acid) methyl, and among these radical initiators, Peroxides are more preferable, and persulfates are particularly preferably used. The amount of the polymerization initiator to be used is 0.01 to 2 parts by weight, 0.02 to 1.5 parts by weight, or 0.05 to 1.0 part by weight, based on 100 parts by weight of the total monomers constituting the carboxylic acid-modified nitrile-based copolymer. Within this range, the polymerization rate is controlled and the final product can be easily produced.

The activator may be selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate, and sodium sulfite.

Examples of the molecular weight modifier include, but are not limited to, mercaptans such as? -Methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, and octyl mercaptan; Halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, and methylene bromide; Containing sulfur compounds such as tetraethylthiuram disulfide, dipentamethylenethiuramdisulfide, diisopropylkisantigen disulfide, and the like. These molecular weight modifiers can be used alone or in combination of two or more. Of these, mercaptans are preferable, and t-dodecyl mercaptan can be more preferably used. The amount of the molecular weight regulator to be used is, for example, 0.1 to 2.0 parts by weight, 0.2 to 1.5 parts by weight or 0.3 to 1.0 parts by weight based on 100 parts by weight of the total monomer constituting the carboxylic acid-modified nitrile-based copolymer. Within this range, the physical properties and polymerization stability of the dip-molded article are remarkably improved.

In addition, it is of course possible to further add a chelating agent, a dispersing agent, a pH adjusting agent, an oxygen scavenger, a particle size regulating agent, an anti-aging agent, and an oxygen scavenger in the polymerization of the latex of the present invention.

The method for introducing the monomer mixture constituting the carboxylic acid-modified nitrile-based copolymer may be, for example, a method in which the monomer mixture is introduced all at once into the polymerization reactor, the monomer mixture is continuously introduced into the polymerization reactor, or a part of the monomer mixture is introduced into the polymerization reactor And the remaining monomers are continuously supplied to the polymerization reactor.

The polymerization temperature during the emulsion polymerization is not particularly limited, but is, for example, from 10 to 90 캜, from 20 to 80 캜 or from 25 to 75 캜.

The conversion rate when the polymerization reaction is stopped is, for example, 90% or more, 90% to 99.9% or 93% to 99%.

The unreacted monomer is removed and the solid content and pH are adjusted to obtain a carboxylic acid-modified nitrile-based copolymer latex.

The glass transition temperature can be adjusted according to the content of the conjugated diene monomer, and the particle diameter or the average particle diameter can be adjusted according to the type and content of the emulsifier.

The latex glass transition temperature is measured by Differential Scanning Calorimetry and the average particle size is measured by a Laser Scattering Analyzer (Nicomp).

2. Styrene-based polymer emulsifier

In the latex composition for dip molding according to the present invention, the styrene-based polymer emulsifier to be mixed with the carboxylic acid-modified nitrile latex has a glass transition temperature of 80 to 150 캜, and a mixture of an ethylenically unsaturated acid monomer and an ethylenically unsaturated monomer is polymerized . Wherein the styrene-based polymer emulsifier comprises 50 to 80% by weight of an ethylenic unsaturated acid monomer, And 20 to 50% by weight of an ethylenically unsaturated monomer.

The ethylenically unsaturated acid monomer may contain at least one acidic group selected from the group consisting of a carboxyl group, a sulfonic acid group and an acid anhydride group. Specific examples of the ethylenic unsaturated acid monomer include ethylenically unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid, itaconic acid and maleic acid; Polycarboxylic anhydrides such as maleic anhydride and citraconic anhydride; Ethylenically unsaturated sulfonic acid monomers such as styrenesulfonic acid; Ethylenically unsaturated polycarboxylic acid partial ester monomers such as monobutyl fumarate, monobutyl maleate, and mono-2-hydroxypropyl maleate; and the like. Of these, acrylic acid is particularly preferable.

The ethylenically unsaturated monomer may also be a vinyl aromatic monomer selected from the group consisting of styrene, alkylstyrene, and vinylnaphthalene; Fluoroalkyl vinyl ethers such as fluoro ethyl vinyl ether; (Meth) acrylamide, N, N-dimethylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide and N-propoxymethyl An ethylenically unsaturated amide monomer selected from the group consisting of: Nonconjugated diene monomers such as vinylpyridine, vinylnorbornene, dicyclopentadiene and 1,4-hexadiene; (Meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, trifluoroethyl (Meth) acrylate, dibutyl fumarate, diethyl maleate, methoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, cyanomethyl Ethyl (meth) acrylate, 2-ethyl-6-cyanohexyl (meth) acrylate, 3-cyanopropyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxy Ethylenically unsaturated carboxylic acid ester monomers selected from the group consisting of glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate and glycidyl (meth) acrylate.

The glass transition temperature of the styrenic polymer emulsifier can be adjusted according to the content of the ethylenic unsaturated acid monomer. The glass transition temperature is measured by Differential Scanning Calorimetry, and the molecular weight is measured by gel permeation chromatography Permeation Chromatography).

3. Latex composition for deep molding

For example, a mixture of the carboxylic acid-modified nitrile-based copolymer latex obtained by the above method and the styrene-based polymer emulsifier is mixed with a pigment such as a vulcanizing agent, an ionic crosslinking agent, titanium oxide, a vulcanization catalyst, a filler such as silica, And at least one additive selected from the group consisting of a pH adjuster such as ammonia or an alkali hydroxide may be mixed to prepare the latex composition for dip molding according to the present invention.

The carboxylic acid-modified nitrile-based copolymer latex having a solid content of 10 to 30% in the latex composition for deep-forming is, for example, 80 to 99% by weight, 85 to 99% by weight or 90 to 99% by weight Is preferable in terms of physical properties of the glove, which is one type of dip-molded article, and the increase of the syneresis time and the reduction of foaming in the manufacturing process of the present invention.

The solid content concentration of the latex latex composition of the present invention is, for example, 10 to 40% by weight, 15 to 35% by weight or 18 to 33% by weight. The pH of the latex latex composition of the present invention is, for example, 8.0 to 12, 9 to 11, or 9.3 to 10.5.

4. Deep molded product

As a dip molding method for obtaining the dip-shaped article of the present invention, a usual method can be used, and examples thereof include a direct dipping method, an anode adhesion dipping method, and a Teague adhesion dipping method. Of these, the positive electrode deposition dipping method is preferable because of the advantage of easily obtaining a dip-shaped article having a uniform thickness. The dip-molded article can be a surgical glove, a test glove, a condom, a catheter, an industrial glove, a household glove, or a health care product.

Hereinafter, a method for producing a dip-molded article using the latex composition of the present invention will be described step by step.

(a) immersing a hand shaped dip forming mold in a coagulant solution and attaching a coagulant to the surface of the dip forming mold

Examples of coagulants include metal halides such as barium chloride, calcium chloride, magnesium chloride, zinc chloride and aluminum chloride, and the like; Nitrates such as barium nitrate, calcium nitrate and zinc nitrate; Acetic acid salts such as barium acetate, calcium acetate and zinc acetate; Calcium sulfate, magnesium sulfate, and sulfate such as aluminum sulfate. Of these, calcium chloride and calcium nitrate are preferred. The coagulant solution is a solution in which the above coagulant is dissolved in water, alcohol or a mixture thereof. The concentration of coagulant in the coagulant solution is usually from 5 to 75% by weight or from 15 to 55% by weight.

(b) immersing a dip molding die with a coagulant on the latex resin composition of the present invention to form a dip molding layer

A hand shaped dip forming die with a coagulant attached thereto is immersed in the latex composition for dip molding of the present invention and then the dip forming die is taken out to form a dip forming layer.

(c) dipping a hand shaped dip forming mold formed in the dip forming mold into the latex resin composition of the present invention to form a double dip forming layer

A hand shaped dip forming die having a dip formed layer is once again immersed in the late forming latex composition of the present invention and then the dip forming die is taken out to form a dip formed layer.

(d) crosslinking the latex resin by heat-treating the dip molding layer formed in the dip molding die

During the heat treatment, the water component first evaporates and crosslinking is effected. Subsequently, the crosslinked dip molding layer is peeled off from the dip molding die to obtain a dip molded article.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Changes and modifications may fall within the scope of the appended claims.

[Example]

Example 1

A 10 L high-pressure reactor equipped with a stirrer, a thermometer, a condenser, an inlet of nitrogen gas, and a monomer, an emulsifier and a polymerization initiator was charged with 25% by weight of acrylonitrile, 1,3-butadiene 70 2.5 parts by weight of sodium alkylbenzenesulfonate, 0.5 part by weight of t-dodecylmercaptan and 140 parts by weight of ion-exchanged water were added to 100 parts by weight of a monomer mixture of 5% by weight and 5% by weight of methacrylic acid.

After the temperature was elevated, 0.25 parts by weight of potassium persulfate as a polymerization initiator was added. When the conversion was 95%, 0.1 part by weight of sodium dimethyldithiocarbamate was added to terminate the polymerization. Unreacted monomers were removed through a deodorization process, and ammonia water, an antioxidant, a defoaming agent and the like were added to obtain a carboxylated acrylonitrile-butadiene copolymer latex having a solid concentration of 45% and a pH of 8.5.

As a result of analysis, the latex was found to have a solid content concentration of 45%, a glass transition temperature of -30 캜, and an average particle diameter of 120 nm, and the prepared latex was referred to as 'latex-A'.

Next, a styrene-based polymer emulsifier (total solid content: 30%) having a glass transition temperature of 120 ° C and a weight average molecular weight of 7,000, which is composed of the latex-A and styrene, alphamethylstyrene and acrylic acid was mixed at a weight ratio of 99: .

(Preparation of composition for dip molding)

A 3% potassium hydroxide solution and an appropriate amount of secondary distilled water were added to the mixture to obtain a composition for dip molding having a solid concentration of 25% and a pH of 10.0.

(Dip molded article production)

22 parts by weight of calcium nitrate, 69.5 parts by weight of distilled water, 8 parts by weight of calcium carbonate and 0.5 part by weight of a wetting agent (Teric 320 produced by Huntsman Corporation, Australia) were mixed to prepare a coagulant solution. A hand-shaped ceramic mold was immersed in this solution for 1 minute, pulled out, dried at 80 ° C for 3 minutes, and the coagulant was applied to the hand mold.

Next, the mold to which the coagulant was applied was immersed in the above-described composition for deep molding for 1 minute and pulled up, and then the mold was dried at 80 캜 to confirm the time for the occurrence of the syneresis. This time is shown in Table 1 below.

Example 2

A glove-shaped deep-molded product was prepared in the same manner as in Example 1, except that the latex A of Example 1 and the styrene-based polymer emulsifier were mixed at a weight ratio of 95: 5 to prepare a mixture. The time of occurrence was confirmed and is shown in Table 1 below.

Example 3

A glove-shaped dip-molded article was prepared in the same manner as in Example 1, except that the latex A of Example 1 and the styrene-based polymer emulsifier were mixed at a weight ratio of 90:10 to prepare a mixture. The time was confirmed and is shown in Table 1 below.

Example 4

The procedure of Example 1 was repeated except that latex A of Example 1 was mixed with a styrenic polymer emulsifier having a glass transition temperature of 120 캜 and a weight average molecular weight of 16,000 at a weight ratio of 99: And the time for the occurrence of the syneresis was confirmed. The results are shown in Table 1 below. ≪ tb > < TABLE >

Comparative Example 1

In the same manner as in Example 1 except that latex-A was used alone in Example 1, a glove-shaped deep-molded product was prepared, and physical properties thereof are shown in Table 1 below.

Comparative Example 2

Except that 1 wt% of sodium dodecylbenzene sulfonate (SDBS) used as an emulsifier was mixed with 99 wt% of latex-A in Example 1 to prepare a glove type dip A molded article was prepared and physical properties thereof are shown in Table 1 below.

Scenery time (s) Example 1 59 Example 2 101 Example 3 215 Example 4 75 Comparative Example 1 50 Comparative Example 2 98

Based on the results shown in Table 1, dip-formed articles (Examples 1 to 4) prepared from a carboxylic acid-modified nitrile latex composition in which a carboxylic acid-modified nitrile-based copolymer latex according to the present invention and a styrene- It can be confirmed that the syneresis time is longer as compared with the dip molded articles prepared in Comparative Examples 1 and 2. [ Also, it was confirmed that the more the amount of the mixed styrenic polymer emulsifier, the longer the duration of the syneresis.

Experimental Example 1

20 g of the mixture of latex-A and styrene-based polymer emulsifier used in Example 1 was placed in a 100 ml measuring cylinder, and the inlet was sealed. The amount of the foam was measured by scaling 50 times, and the results are shown in Table 2 below.

Experimental Example 2

20 g of the mixture of latex-A and styrene-based polymer emulsifier used in Example 2 was placed in a 100 ml measuring cylinder, and the inlet was sealed. The amount of foam was measured by scaling 50 times to measure the amount of bubbles.

Experimental Example 3

20 g of the mixture of the latex-A and styrene-based polymer emulsifier used in Example 3 was placed in a 100 ml measuring cylinder, and the inlet was sealed. The amount of the foam was measured by gradual shaking 50 times, and the results are shown in Table 2 below.

Experimental Example 4

20 g of a mixture of latex-A used in Comparative Example 2 and sodium dodecylbenzenesulfonate used as an emulsifier was placed in a 100 ml measuring cylinder and the inlet was sealed. The amount of the foam was measured by scaling 50 times, .

Bubble generation (cm) Experimental Example 1 1.0 Experimental Example 2 1.4 Experimental Example 3 2.1 Experimental Example 4 10

The latex composition for dip molding according to the present invention as described in Experimental Examples 1 to 3 was prepared by mixing the latex composition of Experimental Example 4 (comparative latex composition) using sodium dodecylbenzenesulfonate, which is a conventional emulsifier, It is possible to provide an excellent working environment because the bubble generation amount is small.

Claims (17)

Carboxylic acid-modified nitrile-based copolymer latex; And
Styrene-based polymer emulsifiers;
Wherein the styrene-based polymer emulsifier comprises 50 to 80% by weight of an ethylenic unsaturated acid monomer, Wherein the monomer mixture comprising 20 to 50% by weight of the ethylenically unsaturated monomer is polymerized. The method according to claim 1,
Wherein the carboxylic acid-modified nitrile-based copolymer constituting the carboxylic acid-modified nitrile-based copolymer latex has a glass transition temperature within a range of -50 ° C to -15 ° C. The method according to claim 1,
Wherein the carboxylic acid-modified nitrile-based copolymer constituting the carboxylic acid-modified nitrile-based copolymer latex has an average particle size of 90 nm to 200 nm. The method according to claim 1,
Wherein the carboxylic acid-modified nitrile-based copolymer constituting the carboxylic acid-modified nitrile-based copolymer latex comprises 40 to 89% by weight of a conjugated diene monomer, 10 to 50% by weight of an ethylenically unsaturated nitrile monomer, and 0.1 to 10 By weight based on the total weight of the latex composition. 5. The method of claim 4,
Wherein the conjugated diene monomer is at least one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and isoprene By weight based on the total weight of the latex composition. 5. The method of claim 4,
Wherein the ethylenically unsaturated nitrile monomer is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile,? -Chloronitrile and? -Cyanoethyl acrylonitrile, ≪ / RTI > 5. The method of claim 4,
Wherein the ethylenically unsaturated acid monomer is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, citraconic anhydride, styrenesulfonic acid, monobutyl fumarate, monobutyl maleate and mono-2-hydroxypropyl maleate Lt; RTI ID = 0.0 > 1, < / RTI > The method according to claim 1,
Wherein the styrene-based polymer emulsifier has a glass transition temperature within a range of 80 to 150 ° C. The method according to claim 1,
Wherein the styrene-based polymer emulsifier has a weight average molecular weight of 1,000 to 50,000. delete The method according to claim 1,
Wherein the ethylenically unsaturated acid monomer is at least one member selected from the group consisting of acrylic acid, methacrylic acid, maleic anhydride, citraconic anhydride, styrenesulfonic acid, monobutyl fumarate, and monobutyl maleate. Composition. The method according to claim 1,
Wherein the ethylenically unsaturated monomer is at least one selected from the group consisting of a vinyl aromatic monomer, a fluoroalkyl vinyl ether, an ethylenically unsaturated amide monomer, a non-conjugated diene monomer and an ethylenically unsaturated carboxylic acid ester monomer. ≪ / RTI > The method according to claim 1,
Wherein the latex composition for deep-forming comprises the carboxylic acid-modified nitrile-based copolymer latex and the styrene-based polymer emulsifier at a weight ratio of 80:20 to 99.9: 0.1. The method according to claim 1,
Wherein the composition further comprises at least one additive selected from the group consisting of a vulcanizing agent, an ionic cross-linking agent, a pigment, a vulcanization catalyst, a filler, a thickener, and a pH adjuster. 90 to 99% by weight of a carboxylic acid-modified nitrile-based copolymer latex comprising a carboxylic acid-modified nitrile-based copolymer having a glass transition temperature of -50 ° C to -15 ° C and an average particle size of 90 nm or more, 1 to 10% by weight of a styrenic polymer emulsifier having a weight average molecular weight within the range of 1,000 to 50,000, wherein the styrenic polymer emulsifier comprises 50 to 80% by weight of an ethylenic unsaturated acid monomer, Wherein the monomer mixture comprising 20 to 50% by weight of the ethylenically unsaturated monomer is polymerized. 15. A dip-formed article produced by dip-molding a latex composition for dip molding according to any one of claims 1 to 9 or 11 to 15. 17. The method of claim 16,
Wherein said dip-molded article is a surgical glove, a test glove, a condom, a catheter, an industrial glove, a household glove or a health care product.